Abstract: | Preparation and Crystal Structure of the First Polymeric Phosphorus Selenide catena-(P4Se4)x Catena-(P4Se4)x was prepared in crystalline form from the elements using iodine as a catalyst, and characterized by means of X-ray diffraction and IR spectroscopy. Single-crystal investigations (space group P21/c, a = 1 119.2(3), b = 728.2(2), c = 1 142.5(3) pm, β = 115.91(2)°, V = 837.5(7) · 106 pm3) revealed parallel chains of P4Se3 hetero-norbornane units linked via Se atoms. Thus, being the first phosphorus selenide which does not contain discrete molecules, catena-(P4Se4)x can be regarded as a polymeric form of α-P4Se4 or as a crystalline modification of vitrous phosphorus selenide. |